Electroanalysis in Biomedical and Pharmaceutical Sciences

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1 Electroanalysis in Biomedical and Pharmaceutical Sciences

2 Monographs in Electrochemistry Series Editor: Fritz Scholz, University of Greifswald, Germany Surprisingly, a large number of important topics in electrochemistry is not covered by up-to-date monographs and series on the market, some topics are even not covered at all. The series Monographs in Electrochemistry fills this gap by publishing indepth monographs written by experienced and distinguished electrochemists, covering both theory and applications. The focus is set on existing as well as emerging methods for researchers, engineers, and practitioners active in the many and often interdisciplinary fields, where electrochemistry plays a key role. These fields will range among others from analytical and environmental sciences to sensors, materials sciences and biochemical research. More information about this series at

3 Sibel A. Ozkan Jean-Michel Kauffmann Petr Zuman in collaboration with Ana Maria Oliveira Brett, Christopher Brett, Bengi Uslu, Philippe Hubert, Eric Rozet, Cobra Parsajoo, Stéphanie Patris, Ahmad Sarakbi Electroanalysis in Biomedical and Pharmaceutical Sciences Voltammetry, Amperometry, Biosensors, Applications

4 Sibel A. Ozkan Faculty of Pharmacy Department of Analytical Chemistry Ankara University Tandogan, Ankara Ankara Turkey Jean-Michel Kauffmann Faculty of Pharmacy Université Libre de Bruxelles Brussels, Belgium Petr Zuman Department of Chemistry and Biomolecular Science Clarkson University Potsdam, New York USA ISSN ISSN (electronic) Monographs in Electrochemistry ISBN ISBN (ebook) DOI / Library of Congress Control Number: Springer Heidelberg New York Dordrecht London Springer-Verlag Berlin Heidelberg 2015 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made. Printed on acid-free paper Springer-Verlag GmbH Berlin Heidelberg is part of Springer Science+Business Media (

5 Preface In the modern pharmaceutical industry, selective, sensitive, and fully validated analytical methods for drug analysis are major tools applied at all stages of drug discovery, development, and production. Fast and effective development of rugged analytical methods is efficiently undertaken with a thorough understanding of their principles, theory, and instrumentation. The main focus of this book is devoted to electroanalytical methods applied to drug compound analysis. New electrode materials, sensors, biosensors, separation methods with EC detection, their theory, advantages, and limitations have been reported. The unique performance, small size, and low cost of electrochemical devices have led to many useful measuring systems. Given the impressive progress in electroanalytical chemistry and its growing impact on drug analysis, this book offers also an up-to-date, easy-to-read presentations of numerous recent applications in drug compound analysis. In preparing this volume, we have tried to find an appropriate balance between theory and practice, between classical and modern methods of electroanalysis, and between electroanalytical methods. Only brief consideration, however, has been given on sampling, method optimization, data analysis, and statistics. This textbook contains nine contemporary chapters, sharing one goal in electroanalysis of pharmaceuticals. In the first chapter, an overview of drug analysis is presented to situate electrochemical methods in their analytical context. Chapter 2 contains polarography and its application on pharmaceuticals. The following chapter includes modern voltammetric methods which are used most frequently in drug analysis (Chap. 3). In Chap. 4, solid electrodes in detail for drug analysis are described. Screen printed electrodes (SPE) are presented for the determination of drug active compounds in Chap. 5, and the next chapter describes electrochemical biosensors used for drug analysis (Chap. 6). Recent developments in the field of separation methods, specifically liquid chromatography (LC) and flow injection analysis (FIA) with electrochemical detection and the hyphenated techniques related with it, are summarized in Chap. 7. Validation of electroanalytical methods v

6 vi Preface in pharmaceutical analysis, necessary parameters, and their calculations are presented in Chap. 8. The last chapter includes examples of electrochemical application on drug assays. Readers from various fields will likely find new ideas and approaches to solve typical analytical problems in this volume. The completion of this book could not have been possible without the help, inspiration, and encouragement from many people. Last but not least, we warmly acknowledge the gracious support of our families, and we are very grateful to them for their understanding and support throughout the entire process of writing and editing. We would like to thank colleagues (Mehmet Gumustas, Sevinc Kurbanoglu, Burcin Palabiyik, Nurgul Karadas, and Burcu D. Topal) of Sibel A Ozkan for their valuable help. We would like to special thanks to Dr. Heike Kahlert who made useful and valuable comments based on a detailed addition to Chap. 8. Finally, we would like to express our sincere gratitude to a unique set of internationally leading authors, who accepted our invitation to join us and committed their valuable time and efforts to guarantee the success of this book. We would like to express our appreciation and special thanks to Fritz Scholz for his accurate and inspired revision and continuous support and enthusiasm in editing this textbook. Ankara, Turkey Brussels, Belgium Potsdam, NY Sibel A. Ozkan Jean-Michel Kauffmann Petr Zuman

7 Authors of Chapters The chapters have been written by the following authors: Chapter 1 Ankara University, Ankara, Turkey Petr Zuman Department of Chemistry, Clarkson University, Potsdam, NY, USA Chapter 2 Ankara University, Ankara, Turkey Petr Zuman Department of Chemistry, Clarkson University, Potsdam, NY, USA Chapter 3 Ankara University, Ankara, Turkey Ana Maria Oliveira-Brett Faculty of Science and Technology, Department of Chemistry, Coimbra University, Coimbra, Portugal Christopher M.A. Brett Faculty of Science and Technology, Department of Chemistry, Coimbra University, Coimbra, Portugal Chapter 4 Ankara University, Ankara, Turkey vii

8 viii Authors of Chapters Christopher M.A. Brett Faculty of Science and Technology, Department of Chemistry, Coimbra University, Coimbra, Portugal Ana Maria Oliveira-Brett Faculty of Science and Technology, Department of Chemistry, Coimbra University, Coimbra, Portugal Chapter 5 Stéphanie Patris Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Université Libre de Bruxelles, Bruxelles, Belgium Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Université Libre de Bruxelles, Bruxelles, Belgium Chapter 6 Cobra Parsajoo Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Université Libre de Bruxelles, Bruxelles, Belgium Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Université Libre de Bruxelles, Bruxelles, Belgium Chapter 7 Ankara University, Ankara, Turkey Bengi Uslu Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey Ahmad Sarakbi Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Universite Libre de Bruxelles, Bruxelles, Belgium Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Universite Libre de Bruxelles, Bruxelles, Belgium Chapter 8 Ankara University, Ankara, TURKEY Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Universite Libre de Bruxelles, Bruxelles, Belgium Philippe Hubert Department of Pharmacy, CIRM, Laboratory of Analytical Chemistry, Université de Liège (ULg), Liège, Belgium Eric Rozet Department of Pharmacy, CIRM, Laboratory of Analytical Chemistry, Université de Liège (ULg), Liège, Belgium

9 Authors of Chapters ix Chapter 9 Bengi Uslu Faculty of Pharmacy, Department of Analytical Chemistry, Ankara University, Ankara, Turkey Ankara University, Ankara, Turkey Jean-Michel Kauffmann Faculty of Pharmacy, Lab. Instrumental Analysis and Bioelectrochemistry, Université Libre de Bruxelles, Bruxelles, Belgium

10 ThiS is a FM Blank Page

11 Contents 1 Introduction Introduction References Polarography in Studies of Pharmaceuticals Principles of Polarography Comparison with Voltammetric Methods Variants of Polarography Record Keeping Supporting Electrolytes The Half-Wave Potentials and Limiting Currents Identification of the Type of the Limiting Current Role of ph Investigation of a New Compound Structure of Organic Compounds and Polarographic Activity Conclusion References Electroanalytical Techniques Most Frequently Used in Drug Analysis Introduction Linear Sweep and Cyclic Voltammetry Step and Pulse Voltammetry Staircase Voltammetry Normal Pulse Voltammetry Differential Pulse Voltammetry Square Wave Voltammetry Alternating Current Voltammetry Stripping Techniques Anodic Stripping Voltammetry Cathodic Stripping Voltammetry Adsorptive Stripping Voltammetry xi

12 xii Contents Abrasive Stripping Voltammetry Potentiometric Stripping Analysis Conclusions References Solid Electrodes in Drug Analysis Introduction Why Solid Electrode Materials? Properties of Solid Electrode Materials Surface Cleaning Pre-treatments Solid Electrode Materials Metal Electrodes Carbon Electrodes Screen-Printed Electrodes Chemically Modified Electrodes Conclusion References Screen-Printed Electrodes (SPE) for Drug Compounds Determination Introduction SPE Properties SPE Modifications SPE Applications (Table 5.1) Unmodified SPE Modified SPE Surface Screen-Printed Electrode and Ascorbic Acid Determination Conclusion References Electrochemical Biosensors for Drug Analysis Introduction Immobilization Techniques Electrochemical-Based Biosensor Amperometry and Voltammetry Potentiometric Biosensors Impedimetric Biosensors References Electrochemical and Hyphenated Electrochemical Detectors in Liquid Chromatography and Flow Injection Systems for Drug Compound Analysis Introduction Basic Analytical Strategy for Implementing an Amperometric Detector Under Hydrodynamic Conditions Basic Theoretical Aspects [1, 52]

13 Contents xiii LC-Amperometric Detection (LC-AD) Wall-Jet Thin-layer Coulometric LC-Pulsed Amperometric Detection (LC-PAD) [53, 54] Hyphenated Techniques for LC and FIA Conclusion References Electroanalytical Method Validation in Pharmaceutical Analysis and Their Applications Method Validation in Drug Assay Using Electroanalytical Techniques Types of Method Validation Electroanalytical Method Validation Characteristics and Their Calculations Validation Characteristics References Applications for Drug Assays Introduction Assay of Drugs Examples of Electrochemical Application Cyclic, Pulsed, and Stripping Voltammetric Methods Using Solid Electrodes in Pharmaceutical Analysis Applications of Polarography in Pharmaceutical Analysis Applications of LC-EC Detection in Pharmaceutical Analysis Biosensors in Pharmaceutical Analysis (See also Chap. 6) Conclusion References About the Authors About the Editor Index

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